JP2008222759A - Gelling agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gelling agent capable of thickening a wide oily base containing a liquid paraffin or a silicone, and capable of forming a gel-shaped composition providing excellent sense of use while having practical dissolving temperature and thickening effects. <P>SOLUTION: The gelling agent is obtained by allowing a specific lysin derivative (component A) to contains an acylamino acid and/or a long-chain fatty acid (component B). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a gel composition comprising a specific lysine derivative (component A), an acylamino acid and / or a long chain fatty acid (component B), and at least one oil agent.

  Conventionally, as a gelling agent of an oily base that does not dissolve in water, generally, a polyamide resin, 12-hydroxystearic acid, fatty acid dextrin, fatty acid inulin, fatty acid glycerin, dibenzylidene-D-sorbitol, acylamino acid ester (patent) Document 1) is known. However, these gelling agents were able to gel a specific oil agent, but could not exhibit gelling ability for a wide variety of oil agents.

  When acylamino acid (Patent Document 2) was used as a gelling agent, the obtained gel-like composition was opaque, and when applied to the skin, it was not smooth and unusable. .

  On the other hand, cosmetics containing N-acyl-L-glutamic acid dibutylamide have been reported as gelling agents that solve these problems (Patent Documents 3 and 4). These are known to gel various oils such as hydrocarbon oils, ester oils, silicone oils and the like. However, it has low solubility in common oils and requires a high temperature of around 150 ° C. when dissolving the gelling agent. Also, the properties of the resulting gel are hard but brittle, so when applied to the skin There was a problem that it was not smooth.

  There is a need for a gelling agent capable of gelling a wide range of oily bases including hydrocarbon oils and silicones and capable of producing a gel-like composition having a practical melting temperature and excellent usability. It was.

JP-A-53-20438 JP 51-91884 A Japanese Patent Laid-Open No. 51-19139 JP 2002-31697 A

  An object of the present invention is to gel a wide range of oily bases including hydrocarbon oils and silicones, and to produce a gel-like composition having a practical melting temperature and an excellent usability. It is to provide an agent.

  As a result of intensive studies in view of the above problems, the present inventors have solved the above problems by using a gelling agent comprising a specific lysine derivative (component A) and an acylamino acid and / or a long chain fatty acid (component B). The present inventors have found that this can be solved and have completed the present invention.

That is, the present invention includes the following aspects.
[1] A gelling agent comprising a lysine derivative (component A) represented by the following general formula (I) and an acylamino acid and / or a long chain fatty acid (component B).
However, R1 represents a linear saturated hydrocarbon group having 11 to 17 carbon atoms. R2 represents a linear or branched hydrocarbon group having 2 to 12 carbon atoms.
[2] The gelling agent according to [1], further comprising N ^ε -lauroyllysine (component C).
[3] The gelling agent according to any one of [1] to [2], wherein the acylamino acid is acylglycine, acylalanine, acylvaline, acylleucine, acylisoleucine, or acylphenylalanine.
[4] A gel composition comprising the gelling agent according to any one of [1] to [3] and at least one oily base.
[5] The gel composition according to [4], further comprising an alkyl alcohol.

  By using a gelling agent containing the specific lysine derivative (component A) of the present invention and an acylamino acid and / or long chain fatty acid (component B), a wide range of oily bases including liquid paraffin, ester oil, and silicone can be gelled. It is an object of the present invention to provide a gelling agent capable of producing a gel composition having a practical melting temperature and excellent usability. A gel having excellent usability and transparency can be provided.

  The gelling agent of the present invention contains a specific lysine derivative (component A) and an acylamino acid and / or a long chain fatty acid (component B).

The specific lysine derivative (component A) of the present invention has a structure represented by the following general formula (I).
However, R1 represents a linear saturated hydrocarbon group having 11 to 17 carbon atoms. R2 represents a linear or branched hydrocarbon group having 2 to 12 carbon atoms.

  The acyl group represented by R1- (CO) is linearly saturated, and is a lauroyl group, myristoyl group, palmitoyl group, or stearoyl group. A lauroyl group is preferable from the viewpoint of imparting smoothness. The hydrocarbon group represented by R2 may be either linear or branched. An ester group having 2 to 12 carbon atoms, such as an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a lauroyl group, or a mixture thereof; is there. From the viewpoint of ease of preparation and smoothness of the resulting gel, an ethyl group, a propyl group, an octyl group, and a lauroyl group are preferred.

The specific lysine derivative (component A) of the present invention can be prepared by a combination of known techniques. For example, N ^ε -acyl lysine can be obtained by a dehydration condensation reaction between a fatty acid and lysine hydrochloride. The acyl lysine alkyl ester can then be obtained by a conventional esterification reaction.

  The amino acid part of the acylamino acid (component B) used in the present invention may be either a neutral amino acid or an acidic amino acid. Glycine, alanine, valine, leucine, isoleucine, and phenylalanine are preferred from the viewpoint that a gel that gives a smooth feeling when used on the skin can be obtained. The acyl group moiety may be linear or branched, and is an acyl group derived from a saturated or unsaturated fatty acid having 8 to 16 carbon atoms. Examples include an octanoyl group, 2-ethyl Hexanoyl group, nonanoyl group, decanoyl group, lauroyl group, myristoyl group, palmitoyl group and the like. In addition to an acyl group of a single composition fatty acid, it may be a mixed fatty acid obtained from nature such as coconut oil fatty acid or an acyl group of a fatty acid (including branched fatty acid) obtained by synthesis. From the viewpoints of obtaining a smooth and easy-to-use gel and excellent transparency, lauroyl groups, 2-ethylhexanoyl groups, and coconut oil fatty acid acyl groups are most preferred.

  The long chain fatty acid (component B) used in the present invention may be either linear or branched, and is a saturated or unsaturated fatty acid having 14 to 18 carbon atoms. Examples are myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid and the like. In addition to fatty acids having a single composition, natural fatty acids such as castor oil fatty acid, olive oil fatty acid, and palm oil fatty acid, or fatty acids (including branched fatty acids) obtained by synthesis may be used. Palmitic acid, stearic acid, palm oil fatty acid, and the like are preferable from the viewpoint of obtaining a smooth and easy-to-use gel and excellent transparency.

  The acylamino acid (component B) of the present invention can be prepared by a combination of known techniques. For example, an N-acylamino acid can be obtained by a Schotten-Baumann reaction in which a long-chain fatty acid chloride and an amino acid are reacted under basic conditions. On the other hand, as the long-chain fatty acid (component B), a commercially available product can be used.

When the gelling agent of the present invention further contains N ^ε -lauroyllysine (C component), the gel can be given good elongation at the time of application and a smooth feel after application. However, from the viewpoint of good usability, the particle size of the C component is preferably 50 microns or less, and more preferably 30 microns or less.

The lysine, which is the amino acid of N ^ε -lauroyl lysine used as the C component of the present invention, can be used in any of the D form, L form, and DL form, but the L form is preferred from the viewpoint of smooth usability. .

  The compounding ratio (mol%) of the A component and the B component of the present invention is 80/20 to 20/80, preferably 60/40 to 20/80. From the viewpoint of a smooth feeling of use, 45/55 to 30/70 is preferable.

  The total amount (% by weight) of the A component and the B component with respect to the entire gelling agent of the present invention is not particularly limited as long as it is gelled. However, from the viewpoint of gel formation, 50 to 100% is preferable and smooth. From the viewpoint of forming a gel, 70 to 99% is more preferable, and 80 to 99% is particularly preferable.

  The blending amount (% by weight) of the C component with respect to the gelling agent (A component + B component) of the present invention is not particularly limited as long as the gel can be formed. From the viewpoints of elongation at the time of application and smooth feel after application, the lower limit is preferably 0.5%, more preferably 1%, still more preferably 2%, and particularly preferably 4%. From the viewpoint of elongation at the time of coating, the upper limit is preferably 500%, and from the viewpoint of not impairing the appearance after coating, the upper limit is more preferably 250%, further preferably 150%, particularly 100%. preferable.

  The oily base used in the gel composition of the present invention is not particularly limited as long as the gelling agent is sufficiently dissolved by heating and forms a gel when cooled to room temperature. As examples, silicones such as dimethylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; fatty acids such as isostearic acid, undecylenic acid, and oleic acid; myristyl myristate Hexyl laurate, decyl oleate, isopropyl myristate, hexyl decyl dimethyloctanoate, glyceryl monostearate, diethyl phthalate, ethylene glycol monostearate, octyl oxystearate, alkyl benzoate, etc. Tells; hydrocarbons such as liquid paraffin, polyisobutene, petrolatum, squalane; oils and fats such as mink oil, cacao oil, palm oil, palm kernel oil, camellia oil, sesame oil, castor oil, olive oil; ethylene, α-olefin, Examples include co-oligomers.

  The blending amount (% by weight) of the gelling agent with respect to the entire gel composition of the present invention is not particularly limited as long as the gel can be formed. The lower limit is preferably 0.5% from the viewpoint of gelation, more preferably 1% from the viewpoint of gel strength, and particularly preferably 1.5% from the viewpoint of high temperature (50 ° C.) stability. From the viewpoint of gel smoothness, the upper limit is preferably 10%, more preferably 7%, and particularly preferably 5%.

  The gel-like composition of the present invention can improve the familiarity of the gel with the skin by adding an alkyl alcohol. The alkyl alcohol used in the present invention is a linear or branched saturated monovalent or polyhydric alcohol having 2 to 18 carbon atoms. Specifically, lower alcohols such as ethyl alcohol and propanol, higher alcohols such as lauryl alcohol, cetyl alcohol, isostearyl alcohol and octyldodecanol, glycerin, sorbitol, ethylene glycol, propylene glycol, butylene glycol and polyethylene glycol And monohydric alcohols. The blending ratio of the alkyl alcohol is not particularly limited as long as the gel composition keeps its form stable. From the viewpoint that the familiarity of the obtained gel with the skin is remarkably exhibited, the amount (% by weight) of the alkyl alcohol based on the gel composition is preferably 0.2 to 45%, preferably 0.5 to 45%. It is more preferable, and 1 to 20% is particularly preferable from the viewpoint that the conformity to the skin is being effectively exhibited without affecting the appearance and the gel strength.

  The gel strength of the gel composition of the present invention can be adjusted by using another gelling agent in combination. Examples of other gelling agents include, but are not limited to, polyamide resins, 12-hydroxystearic acid, sodium stearate, dibenzylidene-D-sorbitol, fatty acid dextrin, fatty acid glycerin, N-2-ethylhexyl-L-glutamic acid Acyl glutamic acid diamides such as dibutylamide and N-lauroyl-L-glutamic acid dibutylamide, acylglutamine esters such as N-lauroyl-L-glutamine isopropyl ester, and the like can be used.

  As a method for producing the gel composition of the present invention, the gelling agent and the oily base are heated to 60 to 100 ° C. while stirring until the mixture forms a uniform solution, and then cooled to obtain the desired gel-like composition. A composition can be obtained. If it dissolves at a low temperature of less than 60 ° C., it may cause a problem in storage stability as a gel. If it dissolves at a temperature higher than 100 ° C., a substance having poor thermal stability or a volatile component is blended. Unfavorable above.

The gel composition of the present invention can be used as a cosmetic as it is or by blending various components used in the cosmetic within a range not inhibiting the effects of the present invention. Examples include various chelating agents, surfactants, various additives, various powders, and antiperspirant active ingredients.

  The cosmetic of the present invention is not particularly limited, but can be used in the form of various gel cosmetics, cream cosmetics, oil cosmetics, pack cosmetics, and the like.

[Example]
EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

<Production Example 1; Production of N ^ε -lauroyl-L-lysine ethyl ester (component A)>
The suspension was suspended in 20.05 g of N ^ε -lauroyl-L-lysine and 250 mL of ethanol, and dry hydrogen chloride gas generated from 300 mL of sulfuric acid and 170 mL of hydrochloric acid was introduced until saturation. During this time, while the flask containing the ethanol solution was cooled in an ice bath, it was occasionally shaken to completely dissolve the flask. The reaction mixture was left overnight. The reaction solution was concentrated under reduced pressure, and 200 mL of ethanol was newly added and concentrated under reduced pressure. This operation was repeated twice, and 250 mL of diethyl ether was added to the final residue and crushed. Diethyl ether was removed by suction filtration, and the product was collected by filtration. This was dissolved in 300 mL of water, and a morpholine aqueous solution in which 53 g / 55 mL of morpholine was dissolved in 70 mL of water was added and stirred well. The precipitated crystals were separated by filtration and dried, and then recrystallized from 250 mL of hexane.

<Production Example 2; Production of N ^ε -lauroyl-L-lysine lauryl ester (component A)>
N-lauroyl-L-lysine (15.35 g), 1-dodecanol (21.0 mL) and p-toluenesulfonic acid monohydrate (17.3 g) were refluxed at 120 ° C. for 2 days with 250 mL of benzene using a Dean-Stark apparatus. The reaction solution was concentrated under reduced pressure, 200 mL of diethyl ether was added to the residue, and the mixture was left in a freezer. The precipitate was suction filtered and dried. This was dissolved in 40 mL of methanol, and 10 mL of morpholine was added thereto and stirred. Crystals deposited on standing in the refrigerator were filtered off and dried.

<Production Example 3; Production of N-lauroyl-L-alanine (component B)>
110 g of L-alanine, 230 g of t-BuOH, and 27% aqueous sodium hydroxide solution are added and dissolved to adjust the pH to 11. It was cooled to 10 ° C., and 269 g of lauroyl chloride and a 27% aqueous sodium hydroxide solution were added dropwise while maintaining the pH at 11. After completion of the reaction, the acylation reaction liquid was neutralized with 75% sulfuric acid, the pH was adjusted to 2, and the aqueous layer was removed by separating into an organic layer and an aqueous layer at 60 ° C. 757 g of water was poured into the obtained oil layer, and after stirring, the aqueous layer was separated again. An appropriate amount of water / T-BuOH mixed solution was added to the oil layer and cooled to obtain 320 g of white crystals. Further, recrystallization from a water / T-BuOH mixture and drying under reduced pressure were performed.

Other acylamino acids were also prepared in the same manner as in Production Example 1.

<Examples 1 to 7, Comparative Examples 1 and 2; Relation between blending ratio of N ^ε -lauroyl L-lysine derivative (component A) and acylamino acid (component B) and gelling ability>
Change the blending ratio of N ^ε -lauroyl-L-lysine ethyl ester (component A) / N-lauroyl-L-alanine (component B) and add to liquid paraffin so as to be 2 wt% as a gelling agent, then heat This was dissolved, allowed to cool to 25 ° C. without stirring, and the properties of the resulting composition were judged. The properties were evaluated as ◎ for a smooth and stretchy gel, ◯ for a relatively smooth gel, △ for a liquid but viscous product, and x for a precipitated or dissolved solution. The results are shown in Table 1.

From the results of Table 1, as a preferable blending ratio of N ^ε -lauroyl-L-lysine ethyl ester (component A) / N-lauroyl-L-alanine (component B) ((component A) / (component B) = 80 From 20/20 to 20/80, particularly from 60/40 to 20/80, it can be seen that this is excellent from the viewpoint of the properties of the gel-like composition obtained at the time of 45/55 to 30/70. The method for producing a gel composition has the advantage that no stirring work is required during cooling.

<Examples 8-14, Comparative Examples 3-13; Gelation Test>
<Geling ability evaluation method>
It was determined whether or not the obtained gel was gelled visually. The gelation ability was evaluated by the minimum concentration of the sample that can be gelled with respect to the target solvent and the minimum gelation concentration (g / l). The evaluation is such that the minimum gelation concentration is 10 g / l or less, ◎◎, 11-20 g / l, ◎, 21-30 g / l, 、 ３, 31-g / l, Δ, or when precipitated or dissolved without gelation. It was. The results are shown in Table 2.

<Method for evaluating gel properties and transparency>
For evaluation of gel properties and gel transparency, the transparency of the gel prepared at the minimum gelation concentration was judged visually. In addition, a small amount was applied to the skin by hand and examined for properties. In the properties, “soft gel” means a smooth gel, “hard gel” means a hard, soft and brittle gel, and “−” means no gelation.

<Preparation of gel>
Using a gelling agent or a comparative compound shown in Table 2, after adding to the target solvent, it was dissolved by heating and stirring at 90 ° C. for 20 minutes, and this was left to cool to 25 ° C. for evaluation. However, the molar ratio of component A / component B was adjusted to 45/55. The results are shown in Table 3.

From Table 3, it can be seen that the example compounds are excellent in terms of gelling ability, transparency, and smooth use feeling. On the other hand, the comparative compound was not preferable in that it did not gel by dissolution and precipitation with respect to the oil agent, or it did not smooth even when gelled.

<Examples 15 to 19, Comparative Example 14; Evaluation of 1,3-butylene glycol-added gel composition>
A gel composition obtained by adding 1,3-butylene glycol to a gelling agent (A / B molar ratio is 40/60), heating and dissolving at 85 ° C., and allowing to cool to 25 ° C. (Numerical values in the table are g) The feel and familiarity with the skin were evaluated by five expert panelists based on the following evaluation criteria, based on the following two points, with no addition.
・ Ease of familiarity with skin (evaluated from 5 points)
Guideline 5: Excellent improvement in skin fit.
4: An improvement is seen in the familiarity with the skin.
3: A slight improvement is seen in the familiarity with the skin.
2: Criteria 1: A feeling of familiarity with skin gets worse

The average score of the evaluation results is 4.1 or more, ◎, 3.1 to 4.0 is ○, 2.1 to 3.0 is Δ, and 2.0 or less is ×. The results are shown in Table 4.

From Table 4, a gel with a favorable feeling of use was obtained while adding 1,3-butylene glycol and maintaining a gel-like form.

<Prescription Example 1; Cleansing Gel>

<Prescription Example 2; Hair Gel>

<Prescription Example 3; Hair Set Gel>

This formulation was a good hair set gel that had a practical melting temperature and a smooth feeling during use, and gave a good elongation during application and a smooth feel after application.

Various gel-like cosmetics and creams that are capable of gelling a wide range of oily bases including hydrocarbon oils and silicones and that have a practical melting temperature and excellent usability with the gelling agent of the present invention. It is extremely significant that it has become possible to provide cosmetics such as cosmetics, oily cosmetics, and pack cosmetics.

Claims (5)

A gelling agent comprising a lysine derivative (component A) represented by the following general formula (I) and an acylamino acid and / or a long-chain fatty acid (component B).
However, R1 represents a linear saturated hydrocarbon group having 11 to 17 carbon atoms. R2 represents a linear or branched hydrocarbon group having 2 to 12 carbon atoms. The gelling agent according to claim 1, further comprising N ^ε -lauroyl lysine (C component). The gelling agent according to any one of claims 1 to 2, wherein the acylamino acid is acylglycine, acylalanine, acylvaline, acylleucine, acylisoleucine, or acylphenylalanine. A gel composition comprising the gelling agent according to any one of claims 1 to 3 and at least one oily base. Furthermore, alkyl gel is contained, The gel-like composition of Claim 4 characterized by the above-mentioned.